CN111019026A - Polypropylene resin for high-isotacticity lithium battery diaphragm and preparation method thereof - Google Patents

Polypropylene resin for high-isotacticity lithium battery diaphragm and preparation method thereof Download PDF

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CN111019026A
CN111019026A CN201911298685.1A CN201911298685A CN111019026A CN 111019026 A CN111019026 A CN 111019026A CN 201911298685 A CN201911298685 A CN 201911298685A CN 111019026 A CN111019026 A CN 111019026A
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polymerization
lithium battery
isotacticity
polypropylene resin
battery diaphragm
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姚春生
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Panjin Haixing Technology Co ltd
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Panjin Haixing Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Medicinal Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention relates to a preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity, which comprises the following steps: adding propylene into a polymerization kettle, stirring and heating to 35-40 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing hydrogen, controlling the polymerization temperature to be 75-80 ℃, the polymerization pressure to be 0.6-0.8 Mpa and the polymerization time to be 120-240 min, and thus obtaining the polypropylene resin for the high-isotacticity lithium battery diaphragm. The polymerization process adopts an intermittent bulk method, and the polypropylene resin particles with isotacticity of more than 98.8% and elastic recovery of more than 90% are obtained by controlling parameters such as the melt index of a product in the polymerization process of 0.3-2.1 g/10min, the polymerization temperature of 75-80 ℃, the polymerization pressure of 0.6-0.8 MPa, the polymerization time of 120-240 min, the dosage of an external electron donor of 10-18% of the total mass of the catalyst and the like, so that the high-performance high-added-value lithium battery diaphragm is produced, and the quality and the film forming rate of the lithium battery diaphragm are well improved.

Description

Polypropylene resin for high-isotacticity lithium battery diaphragm and preparation method thereof
Technical Field
The invention relates to a polypropylene resin for a lithium battery diaphragm with high isotacticity and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Polypropylene, a thermoplastic resin made by polymerizing propylene. The polypropylene is divided into isotactic polypropylene, atactic polypropylene and syndiotactic polypropylene according to the arrangement position of methyl. The methyl groups in the molecular chain are distributed on one side of the main chain, and the polypropylene is called isotactic polypropylene. In general, polypropylene resins produced industrially have about 95% isotactic structure, the remainder being atactic or syndiotactic polypropylene, and industrial products have isotactic products as the main component.
The polypropylene diaphragm is used as a high-end product in the lithium battery diaphragm, has excellent comprehensive performance, particularly has gel-like melt at high temperature, is not melted and collapsed, has excellent safety protection on short circuit and explosion during overcharge or temperature rise, and is the first choice of the lithium battery diaphragm material for power. In the structure of the lithium battery, the diaphragm is one of the key inner layer components, the performance of the diaphragm determines the interface structure, the internal resistance and the like of the battery, the characteristics of the battery, such as capacity, circulation, safety performance and the like, are directly influenced, and the diaphragm with excellent performance has an important effect on improving the comprehensive performance of the battery.
The polypropylene isotacticity, i.e., the isotactic index, is a fraction which cannot be extracted by boiling heptane, i.e., the fraction of highly stereoregular crystalline structures, as a percentage of the total polymer. Therefore, the higher the isotactic index, the higher the stereoregularity. The isotactic index is a key index for processing and producing the lithium battery diaphragm.
The main processes for preparing the polypropylene lithium battery diaphragm include a dry process and a wet process, wherein the dry process is to obtain a highly oriented multilayer structure by crystallizing and annealing a crystalline polymer film prepared by extruding and casting polyolefin resin melt, further stretch the film at a high temperature, strip a crystal interface to form a porous structure, and the required polypropylene has a thick lamellar structure in the synthesis process in order to obtain the high-quality porous structure.
At present, the preparation method of the high isotacticity polypropylene resin for producing the lithium battery diaphragm has few patents and documents. Therefore, it is necessary to develop a preparation method of polypropylene resin for a lithium battery separator with high isotacticity to produce a lithium battery separator with high performance and high added value.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the polypropylene resin for the lithium battery diaphragm with high isotacticity and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity comprises the following steps: adding propylene into a polymerization kettle, stirring and heating to 35-40 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing hydrogen, controlling the polymerization temperature to be 75-80 ℃, the polymerization pressure to be 0.6-0.8 Mpa and the polymerization time to be 120-240 min, and thus obtaining the polypropylene resin for the high-isotacticity lithium battery diaphragm.
As a preferred embodiment of the preparation method of the present invention, the polymerization temperature is 78 ℃, the polymerization pressure is 0.7MPa, and the polymerization time is 180 min.
As a preferred embodiment of the preparation method of the present invention, the amount of the external electron donor is 10-18% of the total mass of the catalyst. In this case, the ratio of the amount of material of TEAL (triethylaluminum) to Donor (external electron Donor) was 30.
As a preferable embodiment of the preparation method, the hydrogen is used in an amount of 2.0-2.5 nm3/h。
The flow rate of the polymer is regulated by the amount of hydrogen added during the polymerization. In practical operation, the concentrations of hydrogen and monomer propylene in the reaction kettle are measured by an analytical instrument, and because it is difficult to directly analyze the composition of liquid in a liquid phase reaction kettle, the molar ratio of hydrogen/monomer propylene in the liquid phase is indirectly controlled by adjusting the molar ratio of hydrogen/monomer propylene in the gas phase in the liquid phase reaction kettle, and the hydrogen adding amount of the reaction kettle is strictly controlled, so that the melt flow rate of the reaction kettle is controlled to be between 0.3 and 2.1g/10 min.
In a preferred embodiment of the preparation method of the present invention, the amount of the cocatalyst is 0.05 to 0.2% by mass of the propylene, and the amount of the supported procatalyst is 0.1 to 0.4% by mass of the propylene.
In a preferred embodiment of the production method of the present invention, the co-catalyst is at least one of trimethylaluminum, triethylaluminum, tri-n-octylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum monochloride, and ethylaluminum dichloride. Triethylaluminium is preferred.
In a preferred embodiment of the preparation method of the present invention, the external electron donor is at least one selected from the group consisting of an aromatic carboxylate compound of methyl benzoate, an aromatic carboxylate compound of ethyl benzoate, a 2, 2, 6, 6-tetramethylpiperidinoamines, dicyclopentyldimethoxysilane, and 1, 3-diethyl-2, 2-dimethoxymethylcyclohexane. Organosiloxanes are preferred.
In a preferred embodiment of the preparation method of the present invention, the supported procatalyst is a Ziegler-Natta catalyst, and the support in the supported procatalyst is at least one of an inorganic oxide and an inorganic chloride. Magnesium ethoxide is preferred.
As a preferred embodiment of the preparation method, acidified ethanol is added to terminate the reaction, the temperature is reduced to room temperature, and the polypropylene resin for the high-isotacticity lithium battery diaphragm is obtained by performing suction filtration and drying on reactants.
As a preferred embodiment of the production method of the present invention, the polymerization system is a batch bulk polymerization.
The preparation method adopts a polyolefin mould test device which is an intermittent bulk polymerization process, does not produce ash or irregular substances, and has pure, scientific, reasonable, simple and feasible product.
The polyolefin mold testing device specifically comprises a raw material metering system, a polymerization system, a cooling water circulation system, an auxiliary control system and a diaphragm vacuum pump. The polymerization system mainly comprises a polymerization reaction kettle, three gas paths, two liquid paths, three catalyst liquid paths and four solvent metering tanks. The polymerization reactor is magnetically coupled and sealed, and the jacket is heated with water, and is equipped with frequency-variable speed regulator, stepless speed regulation, pressure gauge, pressure transmitter, speed sensor, temperature sensor, and heat-removing coil pipes. The volume of the polymerization reaction kettle is 5L, the working temperature is from room temperature to 95 ℃, the maximum working pressure is 1.6Mpa, and the maximum rotating speed is 800 r/min. The jacket heating water bath pot is an inner stainless steel shell and an outer stainless steel shell, a PID instrument controls the temperature, the working volume is 30L, the working temperature is between room temperature and 95 ℃, and the heating power is 4000W. The three gas paths are respectively nitrogen and hydrogen, the other gas path is standby, and the gas paths are provided with mass flow agents to control the accurate quality of the used gas. The solvent metering tank is provided with a differential transmitter for metering the mass of the liquid participating in the reaction. The intelligent differential pressure transmitter outputs 4-20 Ma and is linear 0.1% FS. The air pumping amount of the diaphragm vacuum pump is 16.7L/min, and the vacuum degree is 8 mbar. The polyolefin mould test device is an intermittent polymerization mould test device and is controlled by an operation interface of a DCS (distributed control system).
The polypropylene preparation first requires a systematic replacement. The system replacement adds nitrogen into the polymerization kettle through a DCS operating system, the pressure is 0.8MPa (gauge pressure), the pressure is stabilized for half an hour, if no gas leaks, the vacuum pumping and nitrogen replacement treatment are carried out for three times, and the kettle temperature is kept at 60 ℃; the analysis index of the gas in the system reaches O2≤5mg/kg，H2The polypropylene can be prepared after the requirement that O is less than or equal to 5 mg/kg.
Adding refined polymerization-grade propylene into a polymerization kettle which is qualified after analysis through a DCS (distributed control system), heating a reaction kettle, starting stirring in the kettle, automatically starting a system program when the temperature reaches 35-40 ℃, adding set amounts of a cocatalyst, an external electron donor, a supported main catalyst and high-purity hydrogen, heating to 75-80 ℃ under stirring, and polymerizing for 120-240 min under 0.6-0.8 MPa; then adding a certain amount of acidified ethanol into the polymerization kettle, terminating the polymerization reaction, and opening a cooling system to cool the polymerization kettle; and (3) cooling the temperature of the polymerization kettle to room temperature, discharging from a lower discharge port of the polymerization kettle, and carrying out suction filtration and vacuum drying on the final product to obtain the polypropylene particles.
In a second aspect, the invention provides a polypropylene resin for a lithium battery diaphragm with high isotacticity, which is prepared by the preparation method, wherein the isotacticity of the polypropylene is more than 98.8%, and the melt index of the polypropylene is 0.3-2.1 g/10 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polymerization process adopts an intermittent bulk method, and by controlling parameters such as the melt index of a product in the polymerization reaction process of 0.3-2.1 g/10min, the polymerization reaction temperature of 75-80 ℃, the polymerization reaction pressure of 0.6-0.8 MPa, the polymerization reaction time of 120-240 min, the external electron donor dosage of 10-18% of the total mass of the catalyst and the like, the polypropylene resin particles with the isotacticity of more than 98.8% and the elastic recovery rate of more than 90% are obtained, so that the polypropylene resin particles are used for producing the lithium battery diaphragm with high performance and high added value, the quality and the film forming rate of the lithium battery diaphragm are well improved, and the problem that the lithium battery diaphragm material has high stereoregularity is well solved.
(2) The preparation method of the invention adopts the external electron donor, effectively considers the steps of melt index adjustment and isotacticity adjustment in the polymerization process, and simplifies the difficulty of process control.
(3) The polyolefin mould test device used in the invention is an intermittent bulk polymerization process device, does not produce ash or irregular substances, has pure products, and solves the problem of high ash content of the lithium battery membrane material.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
A preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity comprises the following steps: adopting a polyolefin mold testing device, adding refined polymerization-grade propylene into a polymerization kettle which is qualified in analysis through a DCS (distributed control system) operation system, stirring and heating to 35 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing high-purity hydrogen, controlling the polymerization reaction temperature to be 80 ℃, the polymerization reaction pressure to be 0.7MPa, controlling the polymerization reaction time to be 240min, adding acidified ethanol to terminate the polymerization reaction, opening a cooling system to cool the polymerization reaction kettle, cooling the polymerization kettle to room temperature, discharging from a lower discharge port of the polymerization kettle, and performing suction filtration and drying on reactants to obtain the polypropylene resin for the high-isotacticity lithium battery diaphragm. The external electron donor is used in the presence of catalyst10 percent of the total mass of the agent, and the dosage of the hydrogen is 2.0nm3The catalyst is characterized in that the catalyst promoter accounts for 0.05 percent of the mass of the propylene, the supported main catalyst accounts for 0.2 percent of the mass of the propylene, the catalyst promoter is trimethylaluminum, the external electron donor is an aromatic carboxylic ester compound of methyl benzoate, the supported main catalyst is a Ziegler-Natta catalyst, and the carrier in the supported main catalyst is magnesium ethoxide.
The isotacticity of the polypropylene prepared by the method is 98.8%, and the melt index of the polypropylene is 1.7g/10 min.
Example 2
A preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity comprises the following steps: adopting a polyolefin mold testing device, adding refined polymerization-grade propylene into a polymerization kettle which is qualified in analysis through a DCS (distributed control system) operation system, stirring and heating to 40 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing high-purity hydrogen, controlling the polymerization reaction temperature to be 80 ℃, the polymerization reaction pressure to be 0.8MPa, controlling the polymerization reaction time to be 120min, adding acidified ethanol to terminate the polymerization reaction, opening a cooling system to cool the polymerization reaction kettle, cooling the polymerization kettle to room temperature, discharging from a lower discharge port of the polymerization kettle, and performing suction filtration and drying on reactants to obtain the polypropylene resin for the high-isotacticity lithium battery diaphragm. The dosage of the external electron donor is 18 percent of the total mass of the catalyst, and the dosage of the hydrogen is 2.5nm3The catalyst is prepared from a catalyst carrier, a cocatalyst, a load type main catalyst, a Ziegler-Natta catalyst and magnesium chloride, wherein the consumption of the cocatalyst is 0.1% of the mass of propylene, the consumption of the load type main catalyst is 0.4% of the mass of the propylene, the cocatalyst is triethyl aluminum, an external electron donor is an aromatic carboxylic ester compound of ethyl benzoate, the load type main catalyst is the Ziegler-Natta catalyst, and the carrier in the load type main catalyst is magnesium chloride.
The isotacticity of the polypropylene prepared by the method is 99.1%, and the melt index of the polypropylene is 2.1g/10 min.
Example 3
A preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity comprises the following steps: adopting a polyolefin model test device, analyzing and combining through a DCS (distributed control System) operating systemAdding refined polymer-grade propylene into a polymerization kettle after lattice separation, stirring and heating to 37 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing high-purity hydrogen, controlling the polymerization reaction temperature to be 75 ℃, the polymerization reaction pressure to be 0.7Mpa, the polymerization reaction time to be 240min, adding acidified ethanol to terminate the polymerization reaction, opening a cooling system to cool the polymerization reaction kettle, cooling the polymerization kettle to room temperature, discharging from a lower discharge port of the polymerization kettle, and performing suction filtration and drying on reactants to obtain the polypropylene resin for the high-regularity lithium battery diaphragm. The dosage of the external electron donor is 15 percent of the total mass of the catalyst, and the dosage of the hydrogen is 2.0nm3The catalyst is prepared from the following raw materials, wherein the catalyst is composed of a cocatalyst and a supported main catalyst, the cocatalyst is 0.15% of the mass of propylene, the supported main catalyst is composed of 0.3% of the mass of propylene, the cocatalyst is tri-n-octyl aluminum, the external electron donor is 2, 2, 6, 6-tetramethyl piperidine organic amine, the supported main catalyst is a Ziegler-Natta catalyst, and a carrier in the supported main catalyst is magnesium ethoxide.
The isotacticity of the polypropylene prepared by the method is 98.9%, and the melt index of the polypropylene is 1.98g/10 min.
Example 4
A preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity comprises the following steps: adopting a polyolefin mold testing device, adding refined polymerization-grade propylene into a polymerization kettle which is qualified in analysis through a DCS (distributed control system) operation system, stirring and heating to 37 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing high-purity hydrogen, controlling the polymerization reaction temperature to be 76 ℃, the polymerization reaction pressure to be 0.6MPa, controlling the polymerization reaction time to be 120min, adding acidified ethanol to terminate the polymerization reaction, opening a cooling system to cool the polymerization reaction kettle, cooling the polymerization kettle to room temperature, discharging from a lower discharge port of the polymerization kettle, and performing suction filtration and drying on reactants to obtain the polypropylene resin for the high-isotacticity lithium battery diaphragm. The dosage of the external electron donor is 18 percent of the total mass of the catalyst, and the dosage of the hydrogen is 2.5nm3The using amount of the cocatalyst is 0.2 percent of the mass of the propylene, the using amount of the supported main catalyst is 0.2 percent of the mass of the propylene, and the cocatalyst is monochlorodiethylThe external electron donor is dicyclopentyl dimethoxy silane, the supported main catalyst is Ziegler-Natta catalyst, and the carrier in the supported main catalyst is magnesium chloride.
The isotacticity of the polypropylene prepared by the method is 99.1%, and the melt index of the polypropylene is 2.06g/10 min.
Example 5
A preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity comprises the following steps: adopting a polyolefin mold testing device, adding refined polymerization-grade propylene into a polymerization kettle which is qualified in analysis through a DCS (distributed control system) operation system, stirring and heating to 37 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing high-purity hydrogen, controlling the polymerization reaction temperature to be 78 ℃, the polymerization reaction pressure to be 0.8MPa, controlling the polymerization reaction time to be 130min, adding acidified ethanol to terminate the polymerization reaction, opening a cooling system to cool the polymerization reaction kettle, cooling the polymerization kettle to room temperature, discharging from a lower discharge port of the polymerization kettle, and performing suction filtration and drying on reactants to obtain the polypropylene resin for the high-isotacticity lithium battery diaphragm. The dosage of the external electron donor is 16 percent of the total mass of the catalyst, and the dosage of the hydrogen is 2.2nm3The catalyst is characterized in that the catalyst promoter accounts for 0.18 percent of the mass of the propylene, the supported main catalyst accounts for 0.25 percent of the mass of the propylene, the catalyst promoter is ethyl aluminum dichloride, the external electron donor is dicyclopentyl dimethoxy silane, the supported main catalyst is a Ziegler-Natta catalyst, and the carrier in the supported main catalyst is magnesium ethoxide.
The isotacticity of the polypropylene prepared by the method is 99.3%, and the melt index of the polypropylene is 1.85g/10 min.
Example 6
A preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity comprises the following steps: adopting a polyolefin mould test device, adding refined polymerization-grade propylene into a polymerization kettle which is qualified after analysis through a DCS operation system, stirring and heating to 37 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing high-purity hydrogen, controlling the polymerization temperature to 78 ℃, the polymerization pressure to 0.7Mpa, polymerizingAnd (3) the synthetic reaction time is 200min, adding acidified ethanol to terminate the polymerization reaction, opening a cooling system to cool the polymerization reaction kettle, cooling the polymerization reaction kettle to room temperature, discharging from a lower discharge port of the polymerization kettle, and performing suction filtration and drying on reactants to obtain the polypropylene resin for the high-isotacticity lithium battery diaphragm. The dosage of the external electron donor is 13 percent of the total mass of the catalyst, and the dosage of the hydrogen is 2.3nm3The catalyst is prepared from a supported main catalyst, a cocatalyst and an external electron donor, wherein the amount of the cocatalyst is 0.15% of the mass of propylene, the amount of the supported main catalyst is 0.3% of the mass of the propylene, the cocatalyst is ethyl aluminum dichloride, the external electron donor is 1, 3-diethyl-2, 2-dimethoxy methylcyclohexane, the supported main catalyst is a Ziegler-Natta catalyst, and a carrier in the supported main catalyst is magnesium chloride.
The isotacticity of the polypropylene prepared by the method is 98.8%, and the melt index of the polypropylene is 1.47g/10 min.
Effect example 1
The polypropylene resins prepared in examples 1 to 6 were subjected to performance tests, the test results are shown in table 1, and the tests all adopt conventional test methods in the field.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Index g/10min 1.7 2.1 1.98 2.06 1.85 1.47
Isotactic degree% 98.8 99.1 98.9 99.1 99.3 98.8
Viscosity average molecular weight 104 52.2 49.8 54.7 53.6 55.7 50.7
Thickness μm 20 20 20 20 20 20
Elastic recovery rate% 90.0 91.7 92.4 91.8 93.1 92.6
Porosity% 41 40 42 43 42 42
Air permeability s/100cc 390 475 456 420 438 446
Puncture strength grams 335 320 365 340 355 340
Tensile strength Mpa 142 153 138 147 134 139
Percent MD shrinkage at 90 ℃ for 2h 2 2 2 2 2 2
TD shrinkage% 90 deg.C for 2h 0.2 0.2 0.2 0.2 0.2 0.2
Film formation rate √ √ √ √ √ √
As shown in Table 1, by adopting the preparation method provided by the invention, the melt index of the product in the polymerization reaction process is controlled to be 0.3-2.1 g/10min, the polymerization reaction temperature is 75-80 ℃, the polymerization reaction pressure is 0.6-0.8 Mpa, the polymerization reaction time is 120-240 min, the dosage of the external electron donor is 10% -18% of the total mass of the catalyst, the isotacticity of the prepared polypropylene resin is more than 98.8%, the elastic recovery rate is more than 90%, the polypropylene resin can be used for producing a lithium battery diaphragm with high performance and high added value, and the quality and the film forming rate of the lithium battery diaphragm are well improved.
Effect example 2
In order to investigate the influence of polymerization temperature, polymerization pressure and polymerization time on the performance of polypropylene resin, test groups 1-4 and control groups 1-2 are provided. In the preparation methods of the test groups 1 to 4 and the control groups 1 to 2, only the polymerization temperature, the polymerization pressure and the polymerization time are different, and the other preparation conditions are the same. The polymerization reaction temperature, the polymerization reaction pressure and the polymerization reaction time of the test groups 1-4 and the control groups 1-2 are shown in table 2, and the performance of the polypropylene resin prepared by the test groups 1-4 and the control groups 1-2 is tested, and the test results are shown in table 2.
TABLE 2
Test group 1 Test group 2 Test group 3 Test group 4 Control group 1 Control group 2
Polymerization temperature (. degree. C.) 75 76 78 80 70 85
Polymerization pressure (Mpa) 0.6 0.65 0.7 0.8 0.6 1.0
Polymerization time (min) 120 150 180 240 100 260
Index g/10min 1.72 2.09 1.98 2.06 1.2 2.3
Isotactic degree% 98.9 99.1 99.6 99.2 96.7 97.8
Viscosity average molecular weight 104 52.4 50.1 53.7 54.2 47.1 55.6
Thickness μm 20 20 20 20 20 20
Elastic recovery rate% 90.1 91.3 92.6 91.7 87.3 86.5
Porosity% 42 41 43 43 38 37
Air permeability s/100cc 390 420 475 455 350 362
Puncture strength grams 337 342 365 341 315 319
Tensile strength Mpa 146 150 152 149 140 137
Percent MD shrinkage at 90 ℃ for 2h 2 2 2 2 2 2
TD shrinkage% 90 deg.C for 2h 0.2 0.2 0.2 0.2 0.2 0.2
Film formation rate √ √ √ √ × ×
As shown in Table 2, when the preparation method disclosed by the invention is adopted in the test groups 1-4, the polymerization reaction temperature is 75-80 ℃, the polymerization reaction pressure is 0.6-0.8 Mpa, and the polymerization reaction time is 120-240 min, the isotacticity of the prepared polypropylene resin is more than 98.8%, the elastic recovery rate is more than 90%, and the polypropylene resin can be used for producing a lithium battery diaphragm with high performance and high added value, so that the quality and the film forming rate of the lithium battery diaphragm are well improved. The polymerization temperature, polymerization pressure and polymerization time of the control groups 1-2 were not all within the ranges of the present invention, and the performance of the prepared polypropylene resin was inferior to that of the present invention. The polypropylene resin prepared by the test group 3 has the best performances such as isotacticity and elastic recovery, namely when the polymerization temperature is 78 ℃, the polymerization pressure is 0.7Mpa and the polymerization time is 180min, the prepared polypropylene resin has the best performances.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A preparation method of polypropylene resin for a lithium battery diaphragm with high isotacticity is characterized by comprising the following steps: adding propylene into a polymerization kettle, stirring and heating to 35-40 ℃, adding a cocatalyst, an external electron donor and a supported main catalyst, introducing hydrogen, controlling the polymerization temperature to be 75-80 ℃, the polymerization pressure to be 0.6-0.8 Mpa and the polymerization time to be 120-240 min, and thus obtaining the polypropylene resin for the high-isotacticity lithium battery diaphragm.
2. The method according to claim 1, wherein the polymerization temperature is 78 ℃, the polymerization pressure is 0.7Mpa, and the polymerization time is 180 min.
3. The preparation method of claim 1, wherein the amount of the external electron donor is 10-18% of the total mass of the catalyst.
4. The method according to claim 1, wherein the hydrogen is used in an amount of 2.0 to 2.5nm3/h。
5. The process of claim 1 wherein the cocatalyst is at least one of trimethylaluminum, triethylaluminum, tri-n-octylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum monochloride, and ethylaluminum dichloride.
6. The method according to claim 1, wherein the external electron donor is at least one selected from the group consisting of an aromatic carboxylic acid ester compound of methyl benzoate, an aromatic carboxylic acid ester compound of ethyl benzoate, a 2, 2, 6, 6-tetramethylpiperidinoamines, dicyclopentyldimethoxysilane, and 1, 3-diethyl-2, 2-dimethoxymethylcyclohexane.
7. The method according to claim 1, wherein the supported procatalyst is a Ziegler-Natta catalyst, and the support in the supported procatalyst is at least one of an inorganic oxide and an inorganic chloride.
8. The preparation method of claim 1, wherein acidified ethanol is added to terminate the reaction, the temperature is reduced to room temperature, and the polypropylene resin for the lithium battery separator with high isotacticity is obtained by performing suction filtration and drying on the reactant.
9. The method according to claim 1, wherein the polymerization mode is batch bulk polymerization.
10. A polypropylene resin for a lithium battery separator having an isotacticity of 98.8% or more, which is prepared by the method according to any one of claims 1 to 9, and having a melt index of 0.3 to 2.1g/10 min.
CN201911298685.1A 2019-12-17 2019-12-17 Polypropylene resin for high-isotacticity lithium battery diaphragm and preparation method thereof Pending CN111019026A (en)

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Application publication date: 20200417